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Mikhailov played right wing on the top Soviet line of the 1970s, along with left winger Valeri Kharlamov and center Vladimir Petrov. During Soviet League play, he played in 572 games, scoring a record 428 goals along with 224 assists for a record 652 points.[1]

On the Soviet national team, he played 14 seasons, most of them as captain. He scored over 200 goals with the national team, second only to Alexander Maltsev. He led his team to the Olympic gold medal in 1972 and 1976, a silver medal in 1980, eight IIHF World Championships (1969–71,1973–75,1978,1979), and nine Izvestia championships. Mikhailov's last game with the Soviet National team was played in front of 14,000 people at Luzhniki Ice Palace. His teammates carried him around the rink on their shoulders to a thunderous ovation.[2]

Mikhailov was one of the very few to receive the finest order of the Soviet Union, the Order of Lenin.[3]

Mikhailov became a coach following his retirement from playing. In 1981–1984, 1992–1997, 2002–2005, and in March and November 2006, he was the head coach of SKA (St. Petersburg) (third medalist MHL 1994) and the head coach of CSKA from 1998–2001. From November 2007 to 2009, he was head coach of HC "Metallurg" Novokuznetsk.[4][5]

Under his leadership (1992–1995, 2001–2002), the Russian team won gold medals in the 1993 World Championship for the first time ever, and in 2002 he became vice-champion of the world. He was a coach of the Russian team at the World Championships in 2005 and 2006 and at the Olympic Games in 2006.

Since 2011, together with Vladimir Petrov, Vladislav Tretiak, Georgy Poltavchenko, Sergei Egorov and Artur Chilingarov, he has been a member of the board of trustees of the International Tournament in Ice Hockey Arctic Cup.

He was awarded the Order of Lenin (1978), the Order "For Services to the Fatherland» IV degree (2004), the Red Banner of Labor (1975), the "Badge of Honor" (1972), and the medal "For Labor Valor" (1969).